EP0297364A1 - Electrically conductive thermoplastic moulding compositions, process for their preparation and their use - Google Patents
Electrically conductive thermoplastic moulding compositions, process for their preparation and their use Download PDFInfo
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- EP0297364A1 EP0297364A1 EP88109638A EP88109638A EP0297364A1 EP 0297364 A1 EP0297364 A1 EP 0297364A1 EP 88109638 A EP88109638 A EP 88109638A EP 88109638 A EP88109638 A EP 88109638A EP 0297364 A1 EP0297364 A1 EP 0297364A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/10—Homopolymers or copolymers of unsaturated ethers
Definitions
- thermoplastic molding compositions which, owing to their content of electrically conductive carbon black, have sufficient electrical conductivity in order to be able to produce moldings with satisfactory electrical properties.
- these molding compositions must have a very high carbon black content so that the molded articles made from them obtain the desired electrical properties.
- soot generally leads to significantly reduced mechanical properties in the molding composition.
- thermoplastics Mixtures of incompatible thermoplastics are known from the US patent cited under (1), carbon black being added to one of the two thermoplastics before the mixing process.
- carbon black being added to one of the two thermoplastics before the mixing process.
- the electrical conductivity and the mechanical quality of such mixtures leave something to be desired.
- the object of the invention is therefore to produce a soot-containing thermoplastic molding composition with further improved mechanical properties.
- the molding composition is characterized in that at least one polyvinyl alkyl ether having 1 to 4 carbon atoms in the alkyl group is used as polymer C, which has a weight average molecular weight in the range from 20,000 to 200,000.
- the molding compound contains components A, B and C; preferably it consists of them.
- the molding composition may also contain conventional additives as component D.
- component A of the molding composition according to the invention homopolymers or copolymers of styrene with one of the closely related, in particular methyl-substituted styrenes, in which a methyl radical is present as a substituent on the aromatic ring or on the side chain, are suitable.
- P-Methylstyrene should be mentioned here in particular.
- These copolymers can from the known ratios of styrene or substituted styrene in be produced in a manner known per se.
- styrene polymers are graft copolymers which are prepared by polymerizing styrene or substituted styrene in the presence of a rubber, for example a butadiene polymer or rubber-like styrene-butadiene copolymer.
- the polybutadiene content, based on A, can be 3 to 20% by weight, preferably 5 to 12% by weight.
- the rubber is finely dispersed in a polystyrene phase called a hard matrix.
- the production of such impact-resistant polystyrenes is known to the person skilled in the art. Polystyrenes and polymers of substituted styrenes, like the impact-resistant polystyrenes, are commercially available.
- the viscosity number of component A should be in the range from 60 to 120 ml / g (0.5% in toluene at 23 ° C.).
- copolymers containing 70 to 90% by weight of styrene and 10 to 30% by weight of acrylonitrile such as SAN with VZ from 70 to 110
- graft copolymers of styrene and acrylonitrile on polybutadiene (ABS) All of these products are commercially available.
- carbon black is to be understood to mean microcrystalline, finely divided carbon (cf. plastic dictionary, 7th edition, 1980).
- furnace blacks acetylene blacks, gas blacks and the thermal blacks obtainable by thermal production may be mentioned as suitable.
- the particle sizes are preferably in the range from 0.01 to 0.1 ⁇ m and the surfaces in the range from 102 to 104 m2 / g (BET / ASTM D 3037) with DBP absorptions of 102 to 103 ml / 100 g (ASTM D 2414 ).
- component C of the molding composition according to the invention are polyvinyl alkyl ethers with 1 to 4 carbon atoms in the alkyl radical or mixtures of polyvinyl alkyl ethers.
- Polyvinyl methyl ether or polyvinyl ethyl ether is preferred.
- the weight average molecular weight of the polyvinyl alkyl ethers is in the range from 20,000 to 200,000, preferably from 40,000 to 80,000.
- the molding composition according to the invention can contain, as component D, additives which are typical and customary for components A, B and C.
- additives are: fillers, dyes, pigments, antistatic agents, antioxidants, also flame retardants and in particular the lubricants used for the further processing of the molding composition, e.g. are required in the production of moldings or moldings.
- component D can be used as component D in addition to the rubbers and graft copolymers approved for component A.
- Component D can thus represent at least one block copolymer containing styrene and butadiene or isoprene. This can be selectively hydrogenated so that the double bonds originating from the diene are saturated to more than 90%.
- block copolymers can be represented by linear two-block copolymers or their coupling products, the star-branched block copolymers, the latter being mono- or polymodal.
- Block copolymers from the group of the linear butadiene-styrene two-block copolymers with smeared transition, the linear isoprene-styrene two-block copolymers and the radial butadiene-styrene block copolymers can be particularly suitable, these being 60 to 35% by weight of styrene (remainder diene) in the case of total molecular weights included in the range of 40,000 to 250,000.
- Component D can in particular also be a linear block copolymer consisting of styrene and butadiene with a smeared transition, which has been hydrogenated in a manner known per se, only the double bonds originating from the butadiene monomer component being more than 90%, in particular more than 97%, are saturated.
- Such hydrogenation processes are known per se and can e.g. be carried out by the method described in DE-OS 27 48 884.
- the total styrene content of the block copolymer is in the range from 40 to 60% by weight, preferably 50 to 55% by weight, based on D, and that 5 to 25% by weight.
- % of the block copolymer D is in the form of block polystyrene and the rest of the styrene in 60 to 40% by weight, preferably 50 to 45% by weight of butadiene, is statistically incorporated, the block copolymer D having an average molecular weight (weight average) of 50,000 to 200,000, preferably 75,000 to 150,000.
- the molding composition is produced by mixing components A, B and C and, if appropriate, D by all known methods, but components B and C are preferably first premixed.
- components B and C are preferably first premixed.
- A1 An impact-resistant polystyrene with a polybutadiene content of 7.5% by weight, average particle size of the soft phase 2.7 ⁇ m (average: 50 volume percent of the rubber articles present as a soft phase are above this value and 50 volume percent below this value), containing 0.1% by weight % of a sterically hindered phenol as an antioxidant and 6.9% by weight of white oil as a lubricant, VZ of the hard matrix 70 ml / g.
- B1 conductivity black ®PRINTEX XE2 (Degussa AG) BET surface area (ASTM D 3037): 1000 m2 / g DBP absorption (ASTM D 2414): 370 ml / 100 g
- Components B and C were used in the examples as mixtures in a weight ratio of 1: 1. These mixtures were produced from Printex XE2 and Lutonal M 40 using a Drais turbomixer at 150 ° C. This mixture is referred to in the table as B / C.
- the table also shows the impact strength (SZ) measured on molded test specimens and the volume resistivity (R) values measured on pressed test specimens.
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Abstract
Description
Die Erfindung betrifft eine elektrisch leitende thermoplastische Formmasse enthaltend, jeweils bezogen auf die Formmasse aus A+B+C,
- A 40 bis 98 Gew.% mindestens eines Styrol und/oder substituiertes Styrol enthaltenden Polymerisates,
- B 1 bis 30 Gew.% Ruß und
- C 1 bis 30 Gew.% eines weiteren Polymerisates.
- A 40 to 98% by weight of at least one polymer containing styrene and / or substituted styrene,
- B 1 to 30% by weight of carbon black and
- C 1 to 30% by weight of a further polymer.
Zum Stand der Technik werden genannt
- (1) US-PS 3 591 526 und
- (2) Deutsche Patentanmeldung P 36 43 008.0
- (1) U.S. Patent 3,591,526 and
- (2) German patent application P 36 43 008.0
Es sind bereits verschiedene thermoplastische Formmassen bekannt, die aufgrund ihres Gehalts an elektrisch leitfähigem Ruß eine ausreichende elektrische Leitfähigkeit besitzen, um Formkörper mit befriedigenden elektrischen Eigenschaften herstellen zu können. Diese Formmassen müssen jedoch einen sehr hohen Rußgehalt aufweisen, damit die aus ihnen hergestellten Formkörper die gewünschten elektrischen Eigenschaften erhalten. Ein derart hoher Rußanteil führt aber in der Regel bei der Formmasse zu deutlich verminderten mechanischen Eigenschaften.Various thermoplastic molding compositions are already known which, owing to their content of electrically conductive carbon black, have sufficient electrical conductivity in order to be able to produce moldings with satisfactory electrical properties. However, these molding compositions must have a very high carbon black content so that the molded articles made from them obtain the desired electrical properties. However, such a high proportion of soot generally leads to significantly reduced mechanical properties in the molding composition.
Es sind aus der unter (1) zitierten US-PS Mischungen unverträglicher Thermoplaste bekannt, wobei einem der beiden Thermoplasten vor dem Mischvorgang Ruß zugemischt wurde. Die elektrische Leitfähigkeit und die mechanische Qualität solcher Mischungen lassen jedoch zu wünschen übrig.Mixtures of incompatible thermoplastics are known from the US patent cited under (1), carbon black being added to one of the two thermoplastics before the mixing process. However, the electrical conductivity and the mechanical quality of such mixtures leave something to be desired.
In (2) sind rußhaltige Mischungen zweier unverträglicher Thermoplaste beschrieben, die durch einen Gehalt eines Mischungsvermittlers gekennzeichnet sind und ausreichende mechanische Qualitäten aufweisen.In (2) carbon black-containing mixtures of two incompatible thermoplastics are described, which are characterized by the content of a compounding agent and have sufficient mechanical qualities.
Der Erfindung liegt daher die Aufgabe zugrunde, eine rußhaltige thermoplastische Formmasse mit weiter verbesserten mechanischen Eigenschaften herzustellen.The object of the invention is therefore to produce a soot-containing thermoplastic molding composition with further improved mechanical properties.
Diese Aufgabe wird gelöst durch eine Formmasse gemäß Anspruch 1.This object is achieved by a molding composition according to claim 1.
Die Erfindung betrifft daher eine elektrisch leitende thermoplastische Formmasse enthaltend, jeweils bezogen auf die Formmasse aus A+B+C,
- A 40 bis 98 Gew.% mindestens eines Styrol und/oder substituiertes Styrol enthaltenden Polymerisates,
- B 1 bis 30 Gew.% Ruß und
- C 1 bis 30 Gew.% eines Polymerisates.
- A 40 to 98% by weight of at least one polymer containing styrene and / or substituted styrene,
- B 1 to 30% by weight of carbon black and
- C 1 to 30% by weight of a polymer.
Die Formmasse ist dadurch gekennzeichnet, daß als Polymerisat C mindestens ein Polyvinylalkylether mit 1 bis 4 C-Atomen in der Alkylgruppe verwendet wird, der ein Molekulargewicht (Gewichtsmittel) im Bereich von 20.000 bis 200.000 aufweist.The molding composition is characterized in that at least one polyvinyl alkyl ether having 1 to 4 carbon atoms in the alkyl group is used as polymer C, which has a weight average molecular weight in the range from 20,000 to 200,000.
Nachstehend werden der Aufbau der erfindungsgemäßen Formmasse aus den Komponenten, die Herstellung der Komponenten und die Herstellung der Formmasse beschrieben.The structure of the molding composition according to the invention from the components, the production of the components and the production of the molding composition are described below.
Die Formmasse enthält die Komponenten A, B und C; vorzugsweise besteht sie aus ihnen. Ferner kann die Formmasse als Komponente D übliche Zusatzstoffe enthalten.The molding compound contains components A, B and C; preferably it consists of them. The molding composition may also contain conventional additives as component D.
Bezogen auf die Formmasse aus A+B+C enthält sie:
- A 40 bis 98 Gew.%, vorzugsweise 60 bis 95 Gew.%;
- B 1 bis 30 Gew.%, vorzugsweise 2 bis 10 Gew.%;
- C 1 bis 30 Gew.%, vorzugsweise 2 bis 10 Gew.%.
- A 40 to 98% by weight, preferably 60 to 95% by weight;
- B 1 to 30% by weight, preferably 2 to 10% by weight;
- C 1 to 30% by weight, preferably 2 to 10% by weight.
Bezogen auf 100 Gew.-Teile A+B+C können noch zugegen sein:
- D 0,05 bis 30 Gew.-Teile, vorzugsweise 0,10 bis 10 Gew.-Teile
- D 0.05 to 30 parts by weight, preferably 0.10 to 10 parts by weight
Als Komponente A der erfindungsgemäßen Formmasse kommen Homopolymerisate oder Copolymerisate von Styrol mit einem der eng verwandten, insbesondere methylsubstituierten Styrole in Frage, in denen ein Methylrest als Substituent am aromatischen Ring oder an der Seitenkette vorhanden ist. Hier ist vor allem p-Methylstyrol zu erwähnen. Diese Copolymerisate können aus den bekannten Mengenverhältnissen Styrol bzw. substituiertem Styrol in an sich bekannter Weise hergestellt werden. Als Styrolpolymerisate kommen ferner Pfropfmischpolymerisate in Frage, die durch Polymerisation von Styrol oder substituiertem Styrol in Gegenwart eines Kautschuks, z.B. eines Butadienpolymerisats oder kautschukartigen Styrol-Butadien-Copolymerisats, hergestellt werden. Der Polybutadiengehalt kann, bezogen auf A, 3 bis 20 Gew.%, vorzugsweise 5 bis 12 Gew.%, betragen. Der Kautschuk liegt dabei fein dispergiert in einer als Hartmatrix bezeichneten Polystyrolphase vor. Die Herstellung derartiger schlagfester Polystyrole ist dem Fachmann bekannt. Polystyrole und Polymerisate substituierter Styrole sind, ebenso wie die schlagfesten Polystyrole, im Handel erhältlich. Die Viskositätszahl der Komponente A soll im Bereich von 60 bis 120 ml/g (0,5 %ig in Toluol bei 23°C) liegen.As component A of the molding composition according to the invention, homopolymers or copolymers of styrene with one of the closely related, in particular methyl-substituted styrenes, in which a methyl radical is present as a substituent on the aromatic ring or on the side chain, are suitable. P-Methylstyrene should be mentioned here in particular. These copolymers can from the known ratios of styrene or substituted styrene in be produced in a manner known per se. Other suitable styrene polymers are graft copolymers which are prepared by polymerizing styrene or substituted styrene in the presence of a rubber, for example a butadiene polymer or rubber-like styrene-butadiene copolymer. The polybutadiene content, based on A, can be 3 to 20% by weight, preferably 5 to 12% by weight. The rubber is finely dispersed in a polystyrene phase called a hard matrix. The production of such impact-resistant polystyrenes is known to the person skilled in the art. Polystyrenes and polymers of substituted styrenes, like the impact-resistant polystyrenes, are commercially available. The viscosity number of component A should be in the range from 60 to 120 ml / g (0.5% in toluene at 23 ° C.).
Ferner seien genannt die 70 bis 90 Gew.% Styrol und 10 bis 30 Gew.% Acrylnitril enthaltenden Copolymerisate, wie SAN mit VZ von 70 bis 110, sowie die Pfropfcopolymerisate von Styrol und Acrylnitril auf Polybutadien (ABS). Alle diese Produkte sind im Handel erhältlich.Also worth mentioning are the copolymers containing 70 to 90% by weight of styrene and 10 to 30% by weight of acrylonitrile, such as SAN with VZ from 70 to 110, and the graft copolymers of styrene and acrylonitrile on polybutadiene (ABS). All of these products are commercially available.
Als Ruß im Sinne der vorliegenden Erfindung soll mikrokristalliner, feinteiliger Kohlenstoff verstanden werden (vgl. Kunststofflexikon, 7. Aufl. 1980).For the purposes of the present invention, carbon black is to be understood to mean microcrystalline, finely divided carbon (cf. plastic dictionary, 7th edition, 1980).
Als geeignet seien die Ofenruße, Acetylenruße, Gasruße sowie die durch thermische Herstellung erhältlichen Thermalruße genannt.The furnace blacks, acetylene blacks, gas blacks and the thermal blacks obtainable by thermal production may be mentioned as suitable.
Die Teilchengrößen liegen vorzugsweise im Bereich von 0,01 bis 0,1 µm und die Oberflächen im Bereich von 10² bis 10⁴ m²/g (BET/ASTM D 3037) bei DBP-Absorptionen von 10² bis 10³ ml/100 g (ASTM D 2414).The particle sizes are preferably in the range from 0.01 to 0.1 μm and the surfaces in the range from 10² to 10⁴ m² / g (BET / ASTM D 3037) with DBP absorptions of 10² to 10³ ml / 100 g (ASTM D 2414 ).
Als Komponente C der erfindungsgemäßen Formmasse kommen Polyvinylalkylether mit 1 bis 4 C-Atomen im Alkylrest oder Mischungen von Polyvinylalkylethern in Frage. Bevorzugt wird Polyvinylmethylether oder Polyvinylethylether. Das Molekulargewicht (Gewichtsmittel) der Polyvinylalkylether liegt im Bereich von 20.000 bis 200.000, vorzugsweise von 40.000 bis 80.000.As component C of the molding composition according to the invention are polyvinyl alkyl ethers with 1 to 4 carbon atoms in the alkyl radical or mixtures of polyvinyl alkyl ethers. Polyvinyl methyl ether or polyvinyl ethyl ether is preferred. The weight average molecular weight of the polyvinyl alkyl ethers is in the range from 20,000 to 200,000, preferably from 40,000 to 80,000.
Die erfindungsgemäße Formmasse kann als Komponente D Zusatzstoffe enthalten, die für die Komponenten A, B und C typisch und gebräuchlich sind. Als solche Zusatzstoffe seien beispielsweise genannt: Füllstoffe, Farbstoffe, Pigmente, Antistatika, Antioxidantien, auch Flammschutzmittel und insbesondere die Schmiermittel, die für die Weiterverarbeitung der Formmasse, z.B. bei der Herstellung von Formkörpern bzw. Formteilen erforderlich sind.The molding composition according to the invention can contain, as component D, additives which are typical and customary for components A, B and C. Examples of such additives are: fillers, dyes, pigments, antistatic agents, antioxidants, also flame retardants and in particular the lubricants used for the further processing of the molding composition, e.g. are required in the production of moldings or moldings.
Weiterhin können als Komponente D zusätzlich zu den bei der Komponente A zugelassenen Kautschuken und Pfropfmischpolymerisaten Schlagzähmodifier eingesetzt werden. So kann Komponente D mindestens ein Styrol und Butadien bzw. Isopren enthaltendes Blockcopolymerisat darstellen. Dies kann selektiv hydriert sein, so daß die vom Dien stammenden Doppelbindungen zu mehr als 90 % abgesättigt sind. Diese Blockcopolymerisate können durch lineare Zweiblockcopolymerisate oder deren Kopplungsprodukte, die sternförmig verzweigten Blockcopolymerisate, repräsentiert werden, wobei letztere mono- oder polymodal aufgebaut sein können.Furthermore, impact modifiers can be used as component D in addition to the rubbers and graft copolymers approved for component A. Component D can thus represent at least one block copolymer containing styrene and butadiene or isoprene. This can be selectively hydrogenated so that the double bonds originating from the diene are saturated to more than 90%. These block copolymers can be represented by linear two-block copolymers or their coupling products, the star-branched block copolymers, the latter being mono- or polymodal.
Besonders geeignet können Blockcopolymerisate aus der Gruppe der linearen Butadien-Styrol-Zweiblockcopolymerisate mit verschmiertem Übergang, der linearen Isopren-Styrol-Zweiblockcopolymerisate und der radialen Butadien-Styrol-Blockcopolymeren sein, wobei diese 60 bis 35 Gew.% Styrol (Rest Dien) bei Gesamtmolekulargewichten im Bereich von 40.000 bis 250.000 enthalten.Block copolymers from the group of the linear butadiene-styrene two-block copolymers with smeared transition, the linear isoprene-styrene two-block copolymers and the radial butadiene-styrene block copolymers can be particularly suitable, these being 60 to 35% by weight of styrene (remainder diene) in the case of total molecular weights included in the range of 40,000 to 250,000.
Die Komponente D kann insbesondere auch ein lineares, aus Styrol und Butadien bestehendes, Blockcopolymerisat mit verschmiertem Übergang darstellen, das in an sich bekannter Weise selektiert hydriert worden ist, wobei lediglich die vom Monomerenbaustein Butadien herrührenden Doppelbindungen zu mehr als 90 %, insbesondere zu mehr als 97 %, abgesättigt werden. Derartige Verfahren zur Hydrierung sind an sich bekannt und können z.B. nach dem in der DE-OS 27 48 884 beschriebenen Verfahren durchgeführt werden.Component D can in particular also be a linear block copolymer consisting of styrene and butadiene with a smeared transition, which has been hydrogenated in a manner known per se, only the double bonds originating from the butadiene monomer component being more than 90%, in particular more than 97%, are saturated. Such hydrogenation processes are known per se and can e.g. be carried out by the method described in DE-OS 27 48 884.
Wesentlich für den Aufbau des in Rede stehenden Blockcopolymerisats vor der Hydrierung ist, daß der Gesamtstyrolgehalt des Blockcopolymerisats im Bereich von 40 bis 60 Gew.%, vorzugsweise 50 bis 55 Gew.%, bezogen auf D, liegt, und daß 5 bis 25 Gew.% des Blockcopolymerisats D als Blockpolystyrol vorliegen und der Rest des Styrols in 60 b is 40 Gew.%, vorzugsweise 50 bis 45 Gew.% Butadien, statistisch eingebaut vorliegt, wobei das Blockcopolymerisat D ein mittleres Molekulargewicht (Gewichtsmittel) von 50.000 bis 200.000, vorzugsweise 75.000 bis 150.000 aufweist.It is essential for the structure of the block copolymer in question before the hydrogenation that the total styrene content of the block copolymer is in the range from 40 to 60% by weight, preferably 50 to 55% by weight, based on D, and that 5 to 25% by weight. % of the block copolymer D is in the form of block polystyrene and the rest of the styrene in 60 to 40% by weight, preferably 50 to 45% by weight of butadiene, is statistically incorporated, the block copolymer D having an average molecular weight (weight average) of 50,000 to 200,000, preferably 75,000 to 150,000.
Die Herstellung derartiger Blockcopolymerisate ist an sich bekannt und erfolgt durch anionische Polymerisation von Mischungen aus Butadien und Styrol in Gegenwart von Li-alkylinitiatoren und von allerdings nur geringen Mengen an THF (am besten ohne THF). Sie können z.B. nach dem in der DE-OS 31 06 959 beschriebenen Verfahren hergestellt werden, wobei insbesondere adiabatisch in einer Verfahrensstufe gearbeitet wird (Beispiel 2).The preparation of such block copolymers is known per se and is carried out by anionic polymerization of mixtures of butadiene and styrene in the presence of Li-alkyl initiators and, however, only small amounts of THF (preferably without THF). You can e.g. can be produced by the process described in DE-OS 31 06 959, with adiabatic operation being carried out in one process step (example 2).
Die Herstellung der Formmasse erfolgt durch Mischen der Komponenten A, B und C und gegebenenfalls D nach allen bekannten Methoden, wobei jedoch vorzugsweise zunächst die Komponenten B und C vorgemischt werden. Hierfür kommen Buss-Kneter, Brabender, ZSK-Extruder, Turbomischer, Walzaggregate u.ä. in Frage.The molding composition is produced by mixing components A, B and C and, if appropriate, D by all known methods, but components B and C are preferably first premixed. For this come Buss kneaders, Brabender, ZSK extruders, turbo mixers, rolling units, etc. in question.
Die in der vorliegenden Anmeldung beschriebenen Parameter werden wie folgt bestimmt:
- 1. Schlagzähigkeit, SZ, in [kJ/m²] nach DIN 53 453
- 2. Spezifischer Durchgangswiderstand, R, in [Ω·cm] nach DIN 53 482
- 1. Impact strength, SZ, in [kJ / m²] according to DIN 53 453
- 2. Specific volume resistance, R, in [Ω · cm] according to DIN 53 482
Für die Herstellung erfindungsgemäßer Formmassen und von Vergleichsproben wurden die nachfolgend beschriebenen Produkte verwendet:The products described below were used to produce molding compositions according to the invention and comparative samples:
A¹ Ein schlagfestes Polystyrol mit einem Polybutadiengehalt von 7,5 Gew.%, mittlere Teilchengröße der Weichphase 2,7 µm (Mittelwert: 50 Volumenprozent der als Weichphase vorliegenden Kautschukartikel liegen oberhalb dieses Wertes und 50 Volumenprozent unterhalb dieses Wertes), enthaltend 0,1 Gew.% eines sterisch gehinderten Phenols als Antioxidans und 6,9 Gew.% Weißöl als Schmiermittel, VZ der Hartmatrix 70 ml/g.A¹ An impact-resistant polystyrene with a polybutadiene content of 7.5% by weight, average particle size of the soft phase 2.7 μm (average: 50 volume percent of the rubber articles present as a soft phase are above this value and 50 volume percent below this value), containing 0.1% by weight % of a sterically hindered phenol as an antioxidant and 6.9% by weight of white oil as a lubricant, VZ of the hard matrix 70 ml / g.
B¹ Leitfähigkeitsruß ®PRINTEX XE2 (Degussa AG)
BET-Oberfläche (ASTM D 3037): 1000 m²/g
DBP-Absorption (ASTM D 2414): 370 ml/100 gB¹ conductivity black ®PRINTEX XE2 (Degussa AG)
BET surface area (ASTM D 3037): 1000 m² / g
DBP absorption (ASTM D 2414): 370 ml / 100 g
C¹ Polyvinylmethylether ®Lutonal M 40 der BASF AG
Molekulargewicht 20.000 (Zahlenmittel) bzw. 60.000 (Gewichtsmittel)C¹ polyvinyl methyl ether ® Lutonal M 40 from BASF AG
Molecular weight 20,000 (number average) or 60,000 (weight average)
Die Komponenten B und C wurden in den Beispielen als Mischungen im Gewichtsverhältnis 1:1 angewendet. Diese Mischungen wurden aus Printex XE2 und Lutonal M 40 mittels eines Turbomischers der Fa. Drais bei 150°C hergestellt. Diese Mischung wird in der Tabelle als B/C bezeichnet.Components B and C were used in the examples as mixtures in a weight ratio of 1: 1. These mixtures were produced from Printex XE2 and Lutonal M 40 using a Drais turbomixer at 150 ° C. This mixture is referred to in the table as B / C.
Die Erfindung wird durch die nachfolgenden Beispiele und Vergleichsversuche näher erläutert. Die darin genannten Teile und Prozente beziehen sich, sofern nicht anders angegeben, auf das Gewicht.The invention is explained in more detail by the following examples and comparative experiments. Unless stated otherwise, the parts and percentages therein relate to the weight.
Es wurden Mischungen in den in der Tabelle angegebenen Zusammensetzungen auf einem Weber-Extruder unter den nachfolgenden Bedingungen hergestellt:
Schnecke mit Mischtorpedo
2-Strangdüse
70 UPM
Kunststofftemperatur: 190°C
2 x konfektioniertMixtures in the compositions given in the table were produced on a Weber extruder under the following conditions:
Snail with a mixed torpedo
2-strand nozzle
70 RPM
Plastic temperature: 190 ° C
2 x assembled
In der Tabelle sind auch die an gespritzten Prüfkörpern gemessenen Schlagzähigkeiten (SZ) und die an gepreßten Prüfkörpern gemessenen Werte spezifischen Durchgangswiderstände (R) wiedergegeben.
Den Werten der Tabelle ist zu entnehmen, daß bei gleichem Anteil an Leitfähigkeitsruß (5 Gew.% für Beispiel 1 und Vergleichsversuch I, 20 Gew.% für Beispiel 2 und Vergleichsversuch II) die vorhergehende Behandlung des Leitfähigkeitsrußes mit Polymethylvinylether den damit hergestellten Produkten eine verbesserte Schlagzähigkeit und einen geringeren elektrischen Widerstand verleiht.The values in the table show that with the same proportion of conductivity black (5% by weight for example 1 and comparative test I, 20% by weight for example 2 and comparative test II), the previous treatment of the conductive carbon black with polymethyl vinyl ether improved the products thus produced Impact resistance and lower electrical resistance.
Claims (8)
A 40 bis 98 Gew.% mindestens eines Styrol und/oder substituiertes Styrol enthaltenden Polymerisates,
B 1 bis 30 Gew.% Ruß und
C 1 bis 30 Gew.% eines weiteren Polymerisates,
dadurch gekennzeichnet, daß als Polymerisat C mindestens ein Polyvinylalkylether mit 1 bis 4 C-Atomen in der Alkylgruppe verwendet wird, der ein Molekulargewicht (Gewichtsmittel) im Bereich von 20.000 bis 200.000 aufweist.1. containing electrically conductive thermoplastic molding composition, in each case based on the molding composition of A + B + C,
A 40 to 98% by weight of at least one polymer containing styrene and / or substituted styrene,
B 1 to 30% by weight of carbon black and
C 1 to 30% by weight of a further polymer,
characterized in that at least one polyvinyl alkyl ether having 1 to 4 carbon atoms in the alkyl group is used as polymer C, which has a weight average molecular weight in the range from 20,000 to 200,000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3721124 | 1987-06-26 | ||
| DE19873721124 DE3721124A1 (en) | 1987-06-26 | 1987-06-26 | ELECTRICALLY CONDUCTING THERMOPLASTIC MOLDS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0297364A1 true EP0297364A1 (en) | 1989-01-04 |
Family
ID=6330343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88109638A Withdrawn EP0297364A1 (en) | 1987-06-26 | 1988-06-16 | Electrically conductive thermoplastic moulding compositions, process for their preparation and their use |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0297364A1 (en) |
| DE (1) | DE3721124A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999020685A1 (en) * | 1997-10-17 | 1999-04-29 | The Dow Chemical Company | Compositions of interpolymers of alpha-olefin monomers with one or more vinyl or vinylidene aromatic monomers |
| US6174427B1 (en) | 1998-09-24 | 2001-01-16 | The Dow Chemical Company | Process for the preparation of electromotively coated filled thermoset articles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2571928A (en) * | 1947-11-04 | 1951-10-16 | Standard Oil Dev Co | Resinous compositions comprising a styrene isoolefin copolymer and a vinyl polymer |
-
1987
- 1987-06-26 DE DE19873721124 patent/DE3721124A1/en not_active Withdrawn
-
1988
- 1988-06-16 EP EP88109638A patent/EP0297364A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2571928A (en) * | 1947-11-04 | 1951-10-16 | Standard Oil Dev Co | Resinous compositions comprising a styrene isoolefin copolymer and a vinyl polymer |
Non-Patent Citations (1)
| Title |
|---|
| RUBBER CHEMISTRY AND TECHNOLOGY, Band 51, Nr. 5, November-Dezember 1978, Seiten 1075-1082, American Chemical Society Inc.; T. NISHI: "Application of pulsed NMR to elastomeric composite systems" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999020685A1 (en) * | 1997-10-17 | 1999-04-29 | The Dow Chemical Company | Compositions of interpolymers of alpha-olefin monomers with one or more vinyl or vinylidene aromatic monomers |
| US6380294B1 (en) | 1997-10-17 | 2002-04-30 | The Dow Chemical Company | COMPOSITIONS OF INTERPOLYMERS OF α-OLEFIN MONOMERS WITH ONE OR MORE VINYL OR VINYLIDENE AROMATIC MONOMERS AND/OR ONE OR MORE HINDERED ALIPHATIC OR CYCLOALIPHATIC VINYL OR VINYLIDENE MONOMERS BLENDED WITH A CONDUCTIVE ADDITIVE |
| US6174427B1 (en) | 1998-09-24 | 2001-01-16 | The Dow Chemical Company | Process for the preparation of electromotively coated filled thermoset articles |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3721124A1 (en) | 1989-01-05 |
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